CN114852995A - Electrocatalysis application of black phosphorus-based composite material in construction of horseradish peroxidase sensor - Google Patents

Electrocatalysis application of black phosphorus-based composite material in construction of horseradish peroxidase sensor Download PDF

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CN114852995A
CN114852995A CN202210331413.2A CN202210331413A CN114852995A CN 114852995 A CN114852995 A CN 114852995A CN 202210331413 A CN202210331413 A CN 202210331413A CN 114852995 A CN114852995 A CN 114852995A
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swcnts
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孙伟
李小青
姚昱岑
王宝丽
艾益静
邵波
张程
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Hainan Normal University
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Abstract

The invention relates to preparation of a thin-layer black phosphorus alkene/single-walled carbon nanotube composite material and an electrocatalysis application of the composite material in constructing a horseradish peroxidase electrochemical sensor. A nano composite material is prepared by adopting a liquid phase stripping method and a physical mixing method, is used for modifying horseradish peroxidase to construct an enzyme electrochemical sensor, and is used for electrocatalysis application of trichloroacetic acid, sodium nitrite and hydrogen peroxide. The method mainly comprises the following steps: preparing thin-layer black phosphorus alkene, compounding with a single-walled carbon nanotube, preparing a thin-layer black phosphorus alkene/single-walled carbon nanotube composite material, modifying the composite material on the surface of an ionic liquid electrode, and preparing an enzyme electrochemical sensor with a sandwich structure and an electro-catalysis application thereof. The composite material prepared by the invention has the advantages of large effective area, special appearance, strong conductivity, simple preparation process, sensitive detection and good determination effect, and can improve the stability and the dispersibility of the black phosphorus alkene.

Description

Electrocatalysis application of black phosphorus-based composite material in construction of horseradish peroxidase sensor
Technical Field
The invention belongs to the field of preparation methods and applications of electrochemical sensors, and relates to preparation of black phosphorus olefins (BPNs)/single-walled carbon nanotubes (SWCNTs) composite materials and electrocatalysis application of horseradish peroxidase (HRP) electrochemical sensors constructed by the composite materials.
Background
The Black Phosphorus (BP) is an allotrope of phosphorus, commonly called as phospholene, and two adjacent BP layers are overlapped together through Van der Waals force, and the unique layered structure ensures that the black phosphorus has a plurality of excellent performances, such as controllable direct band gap of layer number, higher carrier mobility, obvious anisotropy and better biocompatibility, and has wide application prospect in the fields of photoelectrochemistry, biomedicine, solar cells, lithium ion batteries/sodium ion batteries, transistors, electronic components and the like. With the intensive research on BP materials, some defects of BP are revealed, the BP has poor stability, and the BP exposed in the air or placed in an aqueous solution in the presence of light can be degraded to generate non-toxic PxOy oxide. Fortunately, by effectively surface functionalizing BP, further degradation of BP can be avoided, resulting in good stability and dispersibility of BP.
The thin-layer BPNs have more outstanding advantages such as strong conductivity, good biocompatibility and the like. On the surface of the BPNs, the modified SWCNTs material can play a role in delaying the degradation of the BPNs. Meanwhile, the BPNs and the SWCNTs are synthesized into the BPNs-SWCNTs composite material by adopting a physical mixing method, and the composite material has the characteristics of SWCNTs, such as good biocompatibility, rapid electron transfer, high surface activity and the like. Therefore, the SWCNTs and the BPNs are compounded to realize the synergistic and synergistic effect of the SWCNTs and the BPNs. On one hand, SWCNTs play a dual role in delaying the degradation of BPNs, on the other hand, the conductivity of the composite material is improved, and a wider application prospect is provided for constructing a novel biosensor.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a thin-layer black phosphorus alkene (BPNs)/single-walled carbon nanotube (SWCNTs) composite material and an electrocatalysis application of the thin-layer black phosphorus alkene (BPNs)/single-walled carbon nanotube (SWCNTs) composite material in constructing a horseradish peroxidase (HRP) electrochemical sensor. The invention provides a synthesis method of a BPNs-SWCNTs nano composite material, wherein the thin-layer functionalized BPNs-SWCNTs nano composite material has a sheet structure of BPNs and a tubular structure of SWCNTs, and the SWCNTs and the BPNs are mutually wound together, so that the composite material has stronger conductive capability, and the dispersity and the stability of the thin-layer BPNs can be improved.
Preferably, the thin layer BPNs-SWCNTs nanocomposite has an effective surface area of 0.182cm 2 ；
Preferably, the BPNs-SWCNTs composites are cross-linked and intertwined with each other, and SWCNTs can adhere to the surface of thin layers of BPNs.
The invention provides a preparation method of the composite material and application of an electrochemical enzyme sensor, which comprises the following steps: (1) mixing BPNPs and NMP, performing ultrasonic treatment for 12 hours in an ice bath, centrifuging, preparing a thin-layer BPNs dispersion, and performing ultrasonic treatment for 4 hours with SWCNTs to prepare a thin-layer BPNs-SWCNTs mixed solution; (2) prepared from graphite powder and ionic liquid (HPPF) 6 ) According to the mass ratio of 2: 1, mixing, grinding, filling the mixture into a glass tube inserted with a copper wire to prepare CILE, taking the CILE as a substrate electrode, and polishing the surface of the electrode before each use; (3) on the basis of the step 2, the CILE and the composite material are placed into a glove box, the glove box is firstly vacuumized, and then N is introduced 2 (ii) a (4) Firstly, dripping BPNs-SWCNTs on the surface of CILE, and airing at room temperature to obtain a BPNs-SWCNTs/CILE modified electrode; dropping HRP on the BPNs-SWCNTs/CILE electrode, and airing at room temperature to obtain an HRP/BPNs-SWCNTs/CILE modified electrode; and (5) performing electrochemical test on the electrode construction three-electrode system obtained in the step (4).
Preferably, the thin layer BPNs-SWCNTs nanocompositeThe dosage of the material is 10 mu L, and the volume ratio of the BPNs to the SWCNTs is 1: 1 and mixing. The BPNs are in a thin-layer sheet structure, the concentration of the HRP is 15.0 mg/mL, and the electrode preparation steps (3) and (4) are all filled with N 2 Is finished in the glove box.
Preferably, the preparation of the composite nano material adopts a liquid phase ultrasonic stripping method and a physical mixing method, the liquid phase ultrasonic stripping method is used for preparing thin-layer BPNs, and the physical mixing method is used for preparing the nano composite material.
Preferably, the dosage of the immobilized enzyme for preparing the modified electrode is 10.0 muL and 15.0 mg/mL, and the preparation is finished by naturally airing.
The invention provides a preparation method of a thin-layer black phosphorus alkene (BPNs)/single-walled carbon nanotube (SWCNTs) composite material and an electro-catalysis application of a horseradish peroxidase (HRP) electrochemical sensor. The thin-layer BPNs-SWCNTs nano composite material provided by the invention has the characteristics of good biocompatibility, rapid electron transfer, high surface activity, smaller thickness of BPNs, larger specific surface area and more active centers. Therefore, the combination of SWCNTs and BPNs can realize the synergistic effect of the SWCNTs and the BPNs. Meanwhile, the conductivity of the composite material can be improved, and the environmental stability and the dispersibility of the BPNs are enhanced. The results of the examples show that the BPNs-SWCNTs composite material modified electrode provided by the invention is 1.0 mmol/L K 3 [Fe(CN) 6 ]And 0.5mol/L KCl mixed solution, performing cyclic voltammetry, and measuring the effective area of the solution to be 0.182cm 2 1.44 times larger than CILE.
Drawings
FIG. 1 is a scanning electron microscope and transmission electron microscope image of BPNs of BPNPs, SWCNTs and thin layer BPNs-SWCNTs nanocomposites prepared in example 1.
FIG. 2 is an X-ray diffraction pattern of the thin layer BPNs-SWCNTs nanocomposite prepared in example 1.
FIG. 3 is a chart of the UV-VIS absorption spectra of example 1HRP and prepared BPNs-SWCNTs-HRP.
FIG. 4 is an infrared spectrum of example 1HRP and the prepared BPNs-SWCNTs composite.
FIG. 5 shows various modifications of the electrode prepared in test example 1Very low at 1.0 mmol/L K 3 [Fe(CN) 6 ]And cyclic voltammograms at different sweep rates in 0.5mol/L KCl mixed electrolyte.
FIG. 6 shows that the BPNs-SWCNTs/CILE modified electrode prepared in test example 1 is 1.0 mmol/L K 3 [Fe(CN) 6 ]And a scan velocity profile in 0.5mol/L KCl mixed electrolyte.
FIG. 7 shows the redox peak current and upsilon of the BPNs-SWCNTs/CILE modified electrode prepared in test example 1 at different sweep rates 1/2 The linear relationship of (c).
FIG. 8 is a cyclic voltammogram of different modified electrodes prepared in test example 2 in 0.1mmol/L Phosphate Buffered Saline (PBS).
FIG. 9 is a graph of the scanning speed of Nafion/HRP/BPNs-SWCNTs/CILE modified electrode prepared in test example 2 in 0.1mmol/L PBS at different pH.
FIG. 10 is a graph of catalytic TCV of Nafion/HRP/BPNs-SWCNTs/CILE modified electrode prepared in test example 3.
FIG. 11 shows NaNO catalyzed by Nafion/HRP/BPNs-SWCNTs/CILE modified electrode prepared in test example 3 2 Curve (c) of (d).
FIG. 12 shows that Nafion/HRP/BPNs-SWCNTs/CILE modified electrode prepared in test example 3 catalyzes H 2 O 2 Curve (c) of (d).
Detailed Description
The invention provides a preparation method of a thin-layer black phosphorus alkene (BPNs)/single-walled carbon nanotube (SWCNTs) composite material and an electrocatalysis application of the thin-layer black phosphorus alkene (BPNs)/single-walled carbon nanotube (SWCNTs) composite material in the construction of a horseradish peroxidase (HRP) electrochemical sensor. The electrochemical enzyme sensor provided by the invention has the advantages of simple preparation method, easy operation and low cost, and can be used for measuring TCA and NaNO 2 And H 2 O 2 The electrochemical enzyme sensor has wide electrochemical detection range and low detection limit.
The effective area of an electrochemical sensing platform (BPNs-SWCNTs/CILE) prepared from the thin-layer BPNs-SWCNTs nano composite material provided by the invention is 0.182cm 2 。
Preferably, the electrochemical enzyme sensor is prepared by filling the electrochemical enzyme sensor with N 2 In a glove box.
In the invention, the preparation method of the thin-layer BPNs-SWCNTs nano composite material and the preparation method of the thin-layer BPNs-SWCNTs/CILE obtained by modifying the electrode preferably comprise the following steps:
firstly, a liquid phase stripping method and a physical mixing method are adopted to prepare the thin-layer BPNs-SWCNTs nano composite material. Then placing the CILE and the composite nano material into a glove box, vacuumizing the glove box, and then introducing N 2 And then, dripping a thin layer of BPNs-SWCNTs on the surface of CILE, and naturally airing to obtain the BPNs-SWCNTs/CILE modified electrode.
In the present invention, the BPNs dispersion is a thin layer BPNs dispersion; the present invention preferably pretreats the BPNPs, and in the present invention, the pretreatments preferably include: the BPNPs solution is sonicated, preferably for 8-12 h, more preferably for 12 h, centrifuged at 10000rmp and 12000rmp for 20 minutes, respectively, and then sonicated directly with SWCNTs for 4 hours.
The invention preferably post-treats the thin layer BPNs-SWCNTs/CILE modified electrode, and in the invention, the post-treatment is preferably natural drying in a glove box at room temperature. And after obtaining the BPNs-SWCNTs/CILE modified electrode, continuously dropwise adding HRP, and naturally airing to obtain the HRP/BPNs-SWCNTs/CILE modified electrode which has the characteristics of large specific surface area and high conductivity.
In the present invention, the preferred concentration of HRP is 15.0 mg/mL, and the preferred volume is 10.0. mu.L.
Finally, dripping Nafion on an HRP/BPNs-SWCNTs/CILE modified electrode to obtain Nafion/HRP/BPNs-SWCNTs/CILE; in the invention, the modified electrode is refrigerated in a refrigerator at 4 ℃ when not used, no special requirement is imposed on the preservation time, and the preservation temperature is under a natural condition.
In the present invention, the HRP volume is preferably 10.0. mu.L. After the modified electrode is obtained, the modified electrode is preferably dried in a glove box at room temperature to obtain the sandwich-structured Nafion/HRP/BPNs-SWCNTs/CILE working electrode. In the invention, the reference electrode is preferably a saturated calomel electrode, and the counter electrode is preferably a platinum wire electrode; the invention has no special requirements on the thickness of the dripping and the specific implementation process of the coating, and the conventional dripping thickness and operation which are well known by the technical personnel in the field can be adopted; in the invention, the drying time is not specifically required, and the drying is carried out.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Firstly, mixing BPNPs and NMP in an ice bath, performing ultrasonic treatment for 12 hours, and then centrifuging for 20 minutes at 10000rmp and 12000rmp respectively to prepare thin-layer BPNs dispersion liquid; mixing BPNs dispersion liquid and SWCNTs by adopting a physical mixing method, and carrying out ultrasonic treatment for 4 hours to prepare a thin-layer BPNs-SWCNTs nano composite material; polishing the surface of the CILE electrode, putting the CILE electrode and the composite material into a glove box, vacuumizing the glove box, and introducing N 2 (ii) a Firstly, the BPNs-SWCNTs nano composite material is dripped on the surface of CILE, and the BPNs-SWCNTs/CILE modified electrode is obtained after natural airing. The preparation methods of other modified electrodes SWCNTs/CILE and BPNs/CILE adopt a coating method, and the BPNs/CILE and BPNs-SWCNTs/CILE electrodes do not need to be stored in a refrigerator at 4 ℃.
FIG. 1 is a scanning electron microscope and a transmission electron microscope image of different materials, wherein A in FIG. 1 is a scanning electron microscope image of a multi-layer BPNPs at a scale of 1 μm, and it can be seen that the BPNPs have a multi-layer sheet structure; b in FIG. 1 is a scanning electron micrograph of SWCNTs at 100 nm on a scale, from which it can be seen that the SWCNTs have a tubular structure; FIG. 1 is a scanning electron microscope image of the BPNs-SWCNTs composite material at a scale of 100 nm, and it can be seen that the two are intertwined and adhered together; in FIG. 1, D is a transmission electron micrograph of BPNs at a scale of 1 μm, and it can be seen that BPNs are lamellar.
FIG. 2 is an XPD diagram of the prepared thin-layer BPNs-SWCNTs nano composite material, the crystallography characteristics of the synthesized composite material are detected by XRD, and the composite material has the characteristic diffraction peak of BPNs and the XRD peak of SWCNTs, which shows that the composite material is successfully compounded.
FIG. 3 is a graph of the ultraviolet-visible absorption spectra of HRP and HRP in the preparation of BPNs-SWCNTs composite material, and it can be clearly seen from FIG. 3 that the Soret absorption bands of the HRP in water (curve a) and the HRP in the BPNs-SWCNTs mixed solution (curve b) are both present at 403.2 nm, which indicates that the HRP is not denatured in the BPNs-SWCNTs composite material, and also indicates that the BPNs-SWCNTs have good biocompatibility.
FIG. 4 is a graph showing the infrared spectra of HRP and HRP in the preparation of the composite material, and it is evident from FIG. 4 that the infrared absorption bands of amide I and amide II in the BPNs-SWCNTs composite material (curve b) of HRP (curve a) and HRP are respectively 1700-1600 cm- -1 And 1600- -1 The positions of the two are basically consistent, which indicates that the HRP keeps the original conformation in the BPNs-SWCNTs.
Test example 1
The SWCNTs/CILE, BPNs/CILE and BPNs-SWCNTs/CILE electrodes prepared in example 1 are used as working electrodes, the saturated calomel electrode is used as a reference electrode, a platinum wire is used as a counter electrode, and the three electrodes are placed in a position of 1.0 mmol/L K 3 [Fe(CN) 6 ]And performing electrochemical performance test by adopting cyclic voltammetry in 0.5mol/L KCl mixed electrolyte.
FIG. 5 shows that the BPNs-SWCNTs/CILE modified electrode prepared in test example 1 is 1mmol/L K 3 [Fe(CN) 6 ]And a cyclic voltammogram at 100 mV/s in 0.5mol/L KCl mixed electrolyte, as shown in FIG. 5, CILE (curve a) has an aligned reversible redox peak with a reduction peak current Ipc of 38.00. mu.A and an oxidation peak current Ipa of 34.39. mu.A. On SWCNTs/CILE (curve b), the redox peak current increased, indicating that SWCNTs have good conductivity. The further increase in the redox peak current in BPNs/CILE (curve c) indicates that BPNs are more promoted than SWCNTs [ Fe (CN) 6 ] 3-/4- Electron transfer rate. The oxidation-reduction peak current is obviously maximum on the BPNs-SWCNTs/CILE (curve d), the reduction peak current and the oxidation peak current are 81.43 mu A and 75.82 mu A respectively, and are increased by 2.14 times and 2.20 times respectively compared with the CILE, because of the synergistic effect of the BPNPs-SWCNTs, the speed of the Fe (CN) 6 ] 3-/4- The electron transfer rate with the electrode surface improves the electrochemical response signal.
FIG. 6 shows that the BPNs-SWCNTs/CILE modified electrode prepared in test example 1 is 1.0 mmol/L K 3 [Fe(CN) 6 ]Different from 0.5mol/L KCl mixed electrolyteAccording to the cyclic voltammetry curve under the sweeping speed, the oxidation-reduction peak potential respectively shifts to the positive direction and the negative direction along with the increase of the sweeping speed, and the oxidation-reduction peak current is gradually increased along with the increase of the sweeping speed.
FIG. 7 shows the redox peak current and upsilon of the prepared BPNs-SWCNTs/CILE modified electrode under different sweep rates 1/2 From FIG. 6, it can be seen that the redox peak current is related to upsilon 1/2 In a good linear relationship.
Example 2
The BPNs-SWCNTs/CILE modified electrode obtained in the example 1; after being dried at room temperature, the HRP is dripped on the BPNs-SWCNTs/CILE electrode to obtain an HRP/BPNs-SWCNTs/CILE modified electrode; and then Nafion is dripped on the electrode, and the modified electrode Nafion/HRP/BPNs-SWCNTs/CILE is prepared after natural airing. The same method is adopted for preparing other modified electrodes Nafion/HRP/CILE, Nafion/HRP/SWCNTs/CILE and Nafion/HRP/BPNs/CILE. All electrodes were not refrigerated in a refrigerator stored at 4 ℃.
Test example 2
The Nafion/HRP/BPNs-SWCNTs/CILE, Nafion/HRP/SWCNTs/CILE and Nafion/HRP/BPNs/CILE electrodes prepared in the example 2 are used as working electrodes, a saturated calomel electrode is used as a reference electrode, a platinum wire is used as a counter electrode, and the three electrodes are placed in 0.1mmol/L PBS for electrochemical performance test by adopting a cyclic voltage method.
FIG. 8 is a cyclic voltammogram of different modified electrodes of example 2 in 0.1mmol/L PBS. No redox peak was present on the plot CILE (curve a) over the scan potential range, indicating that no redox reaction occurred at the electrode surface. Asymmetric redox peaks appear on the Nafion/HRP/CILE (curve b) due to slow direct electron transfer of HRP to the electrode. On Nafion/HRP/SWCNTs/CILE (curve c) and Nafion/HRP/BPNs/CILE (curve d), all redox peak currents increase due to the presence of highly conductive SWCNTs and BPNs on the electrode surface improving the conductivity of the electrode interface with the rate of electron transfer. On Nafion/HRP/BPNs-SWCNTs/CILE (curve e), the redox current signal is obviously increased, an aligned reversible redox peak exists at-0.205 and-0.153V, and the peak-to-peak potential (delta Ep) is 52 mV, which indicates that the electron transfer rate of the HRP is promoted by the presence of the BPNs-SWCNTs composite material with good biocompatibility and high conductivity. The redox peak current ratio (Ipc/Ipa) was 1.23, indicating that the electrochemical process is a quasi-reversible process.
FIG. 9 is a graph showing the pH change of Nafion/HRP/BPNs-SWCNTs/CILE in example 2, and it can be seen that the redox peak potentials gradually move in a negative direction as the pH increases. The maximum redox peak current was shown at pH 4.0.
Test example 3
The Nafion/HRP/BPNs-SWCNTs/CILE electrode prepared in example 2 is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum wire is used as a counter electrode, and the three electrodes are placed in 0.1mmol/L PBS for electro-catalytic performance test by adopting a cyclic voltammetry.
FIG. 10 is a cyclic voltammogram of the electrocatalytic reduction reaction of the modified electrode Nafion/HRP/BPNs-SWCNTs/CILE in example 2 at different concentrations of TCA. With the addition of TCA, a new reduction peak appears near-0.485V, the reduction peak current gradually increases and the oxidation peak current gradually decreases until disappearance, the linear range is 4.0-810.0 mmol/L, and the detection limit is 1.3 mmol/L (3 sigma). The HRP has higher catalytic activity in the BPNs-SWCNTs composite material, and the BPNs-SWCNTs have good biocompatibility.
FIG. 11 shows the Nafion/HRP/BPNs-SWCNTs/CILE modified electrode of example 2 at different concentrations of NaNO 2 Cyclic voltammogram of the electrocatalytic reduction reaction of (1). With NaNO 2 With the addition of (2), a new reduction peak appears near-0.460V, and with NaNO 2 The reduction peak current is obviously increased and the oxidation peak current is gradually reduced when the adding amount is increased, and when NaNO is added 2 When the concentration range of (1) is 0.8-49.6 mmol/L, the catalytic reduction peak current and NaNO 2 When the concentration of NaNO is linear 2 When the concentration of (2) is more than 49.6 mmol/L, the reduction peak current is kept almost unchanged, and the detection limit is 0.27 mmol/L (3 sigma). Apparent Michaelis constant (K) M app ) 8.37 mmol/L, which indicates that Nafion/HRP/BPNs-SWCNTs/CILE is applied to NaNO 2 Has good electrocatalytic performance.
FIG. 12 shows an embodiment2 modified electrode Nafion/HRP/BPNs-SWCNTs/CILE at different concentrations H 2 O 2 Cyclic voltammogram of the electrocatalytic reduction reaction of (1). Reduction peak current with H 2 O 2 The concentration is increased, and when the concentration is in the range of 1.0-40.0 mmol/L, the reduction peak current and H are increased 2 O 2 The concentration presents a good linear relation, the detection limit is 0.33 mmol/L (3 sigma), K M app 7.88 mmol/L, which indicates that Nafion/HRP/BPNs-SWCNTs/CILE is relative to H 2 O 2 The HRP has good electrocatalysis effect, and the BPNs-SWCNTs composite material keeps good biological activity.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.

Claims (8)

1. Preparation of thin-layer black phosphorus alkene (BPNs)/single-wall carbon nano tubes (SWCNTs) composite material and electrocatalysis application of horseradish peroxidase (HRP) electrochemical sensor construction,
the method is characterized by comprising the following steps:
(a) respectively preparing trichloroacetic acid, sodium nitrite and hydrogen peroxide solution;
(b) preparation of ionic liquid modified carbon paste electrode (CILE)
1.6 g of graphite powder and 0.8 g N-hexylpyridinium Hexafluorophosphate (HPPF) 6 ) Mixing, grinding uniformly by using a mortar, filling into a glass electrode tube with the diameter of 4mm, compacting, inserting a copper wire as a lead of an electrode, wherein the prepared electrode is an ionic liquid modified carbon paste electrode (CILE), and before use, polishing the surface of the electrode on polishing paper into a mirror surface;
(c) taking Nafion/HRP/BPNs-SWCNTs/CILE as a working electrode, a platinum wire as a counter electrode and silver/silver chloride as a reference electrode, carrying out electrocatalysis performance test by a cyclic voltammetry method, detecting the relationship between the oxidation peak current values and the concentrations of trichloroacetic acid, sodium nitrite and hydrogen peroxide solutions with different concentrations in a phosphate buffer solution to establish a standard curve,
(d) according to the established standard curve, the detection range, the detection limit and the apparent Michaelis constant are obtained,
the modified electrode Nafion/HRP/BPNs-SWCNTs/CILE is prepared by the following steps:
(1) preparation of thin-layer BPNs-SWCNTs nano composite material
Mixing multiple layers of black phosphorus (BPNPs) and N-methylpyrrolidone (NMP) in an ice bath by adopting a liquid phase stripping method and a physical mixing method, and carrying out ultrasonic treatment for 12 hours to prepare thin-layer BPNs dispersion liquid; mixing the BPNs dispersion liquid with SWCNTs according to a volume ratio of 1: 1, mixing, performing ultrasonic treatment for 4 hours in an oxygen-isolated environment to prepare a thin-layer BPNs-SWCNTs nano composite material,
(2) in the glove box, CILE and composite material are put in, the air outlet valve is opened to close the air inlet valve, the vacuum pump is used for vacuum pumping, then the air inlet valve is opened to close the air outlet valve, nitrogen is introduced,
(3) dripping the BPNs-SWCNTs composite material on the surface of CILE to obtain a BPNs-SWCNTs/CILE modified electrode,
(4) dropping HRP on the BPNs-SWCNTs/CILE electrode, naturally airing to obtain an HRP/BPNs-SWCNTs/CILE modified electrode,
(5) and (3) dropwise adding Nafion to the HRP/BPNs-SWCNTs/CILE, and naturally airing to prepare the modified electrode Nafion/HRP/BPNs-SWCNTs/CILE with the sandwich structure.
2. The preparation of the BPNs-SWCNTs nanocomposite material according to claim 1 and the application of HRP modified electrodes in electrocatalysis of electrochemical sensors;
characterized in that the BPNPs used in step (1) are 5.0 mL and 1.0 mg/mL, and are mixed with NMP according to the volume ratio of 1: 1 mixing and carrying out liquid phase ultrasonic stripping; the volume ratio of SWCNTs used in the step 2 is 0.5 mg/mL, and the volume ratio of BPNs to SWCNTs is 1: 1, mixing and ultrasonic processing; the amount of BPNs-SWCNTs used in step (3) is 10.0. mu.L, the amount of HRP used is 10.0. mu.L and 15.0 mg/mL, and the amount of Nafion used in step (5) is 10.0. mu.L and 0.5%.
3. The preparation of the BPNs-SWCNTs nanocomposite material and the application of the HRP modified electrode in the electrocatalysis of an electrochemical sensor according to claim 1, wherein the preparation method comprises the following steps: the thin layer BPNs used were made from multiple layers of black phosphorus by ultrasonic 12 hour stripping in an ice bath.
4. The preparation of the BPNs-SWCNTs nanocomposite material and the application of the HRP modified electrode in the electrocatalysis of an electrochemical sensor according to claim 1, wherein the preparation method comprises the following steps: the BPNs-SWCNTs composite material used in the step (3) is prepared by performing ultrasonic treatment on thin-layer BPNs and SWCNTs for 4 hours in an oxygen-isolated environment.
5. The preparation of the BPNs-SWCNTs nanocomposite material and the application of the HRP modified electrode in the electrocatalysis of an electrochemical sensor according to claim 1, wherein the preparation method comprises the following steps: in the steps (2) to (5), N is charged 2 In a glove box.
6. The preparation of the BPNs-SWCNTs nanocomposite material and the application of the HRP modified electrode in the electrocatalysis of an electrochemical sensor according to claim 1, wherein the preparation method comprises the following steps: a liquid phase ultrasonic stripping method and a physical mixing method used in the step (1).
7. The preparation of the BPNs-SWCNTs nanocomposite and the application of HRP modified electrode in electrochemical sensors according to claim 1, wherein: the steps (3) to (5) adopt a layer-by-layer coating method;
fixing a thin layer of BPNs-SWCNTs nano composite material on CILE, dripping HRP on the BPNs-SWCNTs nano composite material, and dripping Nafion to obtain the enzyme sensor with the sandwich structure.
8. Preparation of the BPNs-SWCNTs nanocomposites according to any of claims 1-7 and electrocatalytic application of HRP modified electrodes in electrochemical sensors.
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